Supramolecular environment-dependent electronic properties of metal-organic interfaces

Model donor-acceptor assemblies at metal-organic interfaces, namely, fluorinated copper-phthalocyanines (F 16CuPC) and pentacene (PEN) assemblies on the Au(111) surface, have been the focus of the present study. A full picture of the crystallographic and electronic structure of PEN and F 16CuPC monolayers as well as of their 1:1 binary mixture on the Au(111) surface has been explored by means of a variety of surface-sensitive techniques, providing important information on the intermolecular and molecule-substrate interactions governing the self-assembly process. A long-range ordered donor-acceptor network is observed for the mixture as a result of the greatly enhanced intermolecular interaction via C-F···H-C hydrogen bonds. Interestingly, the new supramolecular structure involves changes in the electronic structure of the molecular components. In particular, the strongest changes are observed at the C and F atoms of the F 16CuPc, as opposed to the F 16CuPc N, Cu, or PEN C atoms. With the aid of theoretical calculations, such effects are found to be at least partially related to an upward shift in energy of the F 16CuPc molecular orbitals, concomitant with a molecule-to-metal charge donation, not from the HOMO, but deeper lying orbitals. © 2012 American Chemical Society.This work was supported by the Spanish MICINN (MAT2010-21156-C03-01, C03-03, PIB2010US-00652) and the Basque Government (IT-257-07). The SRC is funded by the National Science Foundation (award no. DMR-0084402). B.P.D. thanks the ICTP (Trieste) for travel funding. The research leading to these results has received funding from the European Community’s Seventh Framework Programme (FP7/2007-2013) under grant agreement no. 226716. The research leading to these results has received funding from the European Community’s Seventh Framework Programme (FP7/2007- 2013) through the Integrated Infrastructure Initiative “European Light Sources Activities − Synchrotrons and Free Electron Lasers” (grant agreement no. 226716).Peer Reviewe